Hair cosmetic material

ABSTRACT

A hair set retaining cosmetic material comprising a polymer complex prepared by (1) reacting an amino group containing polysiloxane having the formula: 
     
         A.sub.m R.sub.3-m SiO(R.sub.2 SiO).sub.x (QRSiO).sub.y SiR.sub.3-n A.sub.n 
    
     wherein A is selected from the group consisting of a hydroxyl group, an alkoxy group, and an amino group containing alkylether group; R is selected from the group consisting of an alkyl group having 1 to 18 carbon atoms and a hydroxyl group; Q represents an amino containing alkyl group; m and n each represent a number of 0 to 3; x represents a number of 30 to 400; and y represents a number of 1 to 30 with an anionic group containing polymer; and (2) neutralizing a reaction product of step (1) with an alkaline compound to a neutralization ratio of 60-150%.

This is a continuation of application Ser. No. 07/929,376 filed on Aug.14, 1992, now abandoned.

FIELD OF THE INVENTION

This invention relates to a hair cosmetic material which gives hairglossiness, smoothness to the touch, ease of combing, flexibility ornon-stiffness and, in addition, has good hair set retention and storagestability.

PRIOR ART

A hair cosmetic material such as hair setting lotion, hair spray andhair styling spray or mist typically contains a film forming polymer asa main component. For example, the following polymers have been proposedfor such purposes:

1-ethenyl-2-pyrrolidinone,homopolymer

1-ethenyl-2-pyrrolidinone, copolymer with acetic acid, ethyl ester

ethene, methoxy-, copolymer with but-2-ene-1,4-dioic acid mono ethyl ormono butyl ester

acetic acid, ethenyl ester, homopolymer carboxylated

2-butenoic acid, copolymer with acetic acid, ethenyl ester

alkyl 2-propenoate, copolymer with alkyl 2-methyl-2-propenoate

1-(hydroxymethyl)-5,5-dimethyl hydantoin, homopolymer

dialkylamino alkyl 2-methyl-2-propenoate, homopolymer quaternized

1-ethenyl-2-pyrrolidinone, copolymer with dialkyamino alkyl2-methyl-2-propenoate

2-hydroxyethyl cellulose, quaternary ammonium modified

cationic polysaccharide

1-ethenyl-2-pyrrolidinone, homopolymer quaternized

siliconized cationic polymer

quaternized polyurethane

1-ethenyl-2-pyrrolidinone, copolymer with 2-(dimethylamino)ethyl2-methyl-2-propenoate, compound with dialkyl sulfate

quaternary ammonium salt and quaternary sulfonic acid salt containingpolymer or copolymer

3-(dimethylamino)propyl 2-methyl-2-propenoate, homopolymer or copolymercompound with dialkyl sulfate

carboxylic acid (salt) containing monomer, copolymer with tertiarynitrogen containing monomer

2-propenoic acid, copolymer with vinyl pyridine

quaternized carboxylic acid (salt) containing monomer, copolymer withtertiary nitrogen containing monomer

octyl acrylicamide, acrylate, butylaminoethyl methacrylate, acrylic acidcopolymer

carboxyl group and quaternary ammonium salt containing monomer, polymeror copolymer

N-methacryloyl-N,N'-dimethyl ammonium α-N methylcarboxylicbetainemethacrylic acid alkylester copolymer

However, these polymers or copolymers exhibit an insufficient hair setretaining property and/or give hair poor gloss or lack smoothness orsoftness to the touch. In some hair formulations, they give hair asticky or starchy feeling.

To improve the above deficiencies, it has been suggested that theabove-mentioned hair set polymers be used in combination with an oil,ester oil and hydrocarbon oil. However, these combinations give hair agreasy, oily feeling and exhibit poor hair set retaining ability.

Since the oils are incompatible with water, surface active agents mustbe used which results in hair with poor feel.

Another way to improve the above deficiencies, is to employ thecombination of an amino group containing organodimethyl polysiloxanewith a cationic surface active agent and an amphoteric polymer. Thispolysiloxane has good properties such as giving hair gloss, goodcompatibility with water and imparts smoothness to hair. (Japanese laidopen patent No. 01-190619).

As a hair set retaining polymer, an anionic polymer is desirable sinceit exhibits good hair set retaining capability and an amphoteric polymeris not suitable since it exhibits poor hair set retaining capability,hence, they are not usually used as a hair set polymer.

It is presumed that above JP-01-190619 was proposed because thecombination of amino siloxane with anionic polymer forms a gel whichprecipitates and the combination of aminosiloxane with amphotericpolymer does not result in such gelation or precipitation.

Cationic polymers exhibit insufficient hair set property.

There is an on-going need for a hair cosmetic material having propertiessuch as good fitness with hair, hair glossiness, smoothness of the hairto touch, ease of combing and flexible (non-stiff) finish which areassociated with amino group containing organopolysiloxanes and otherdesirable hair set retaining properties which are associated with theanionic polymer, without the adverse effect of gelation orprecipitation.

SUMMARY IF THE INVENTION

It is an object of this invention to provide a hair cosmetic havingexcellent hair set retaining property.

A hair cosmetic material of the invention is characterized by a polymercomplex prepared by (1) reacting an amino group containing polysiloxaneexpressed by the following general formula.

    A.sub.m R.sub.3-m SiO(R.sub.2 SiO).sub.x (QRSiO).sub.y SiR.sub.3-n A.sub.n

wherein

A is selected from the group consisting of a hydroxyl group, an alkoxygroup, and an amino containing alkylether group;

R is selected from the group consisting of an alkyl group having 1 to 18carbon atoms and a hydroxyl group;

Q represents an amino containing alkyl group;

m and n each represent a number of 0-3;

x represents a number of 30-400; and

y represents a number of 1-30

with an anionic group polymer, and then (2) neutralizing a reactionproduct of step (1) with an alkaline compound for a neutralization ratioof 60-150%.

DETAILED DESCRIPTION OF THE INVENTION

It has been conventionally known that the combination of a cationicpolymer (amino group containing organopolysiloxane exhibit weak cationicproperty) with anionic polymer forms a gel in the solvent which gelprecipitates, and hence, the two components are not used as a haircosmetic material.

However, the inventors of this invention have discovered that it ispossible to produce a soluble copolymer complex by reacting a specificmolecular structure aminopolysiloxane with a specific anionic polymerwhich, if followed by neutralization of copolymer complex eliminates gelformation or precipitation and the copolymer so formed has excellentcosmetic hair properties.

That is, the present invention provides a hair set retaining cosmeticmaterial comprising a polymer complex prepared by (1) reacting aminogroup containing polysiloxane of the general formula:

    A.sub.m R.sub.3-m SiO(R.sub.2 SiO).sub.x (QRSiO).sub.y SiR.sub.3-n A.sub.n

wherein

A is selected from the group consisting of a hydroxyl group, an alkoxygroup, and an amino group containing alkylether group;

R is selected from the group consisting of an alkyl group having 1 to 18carbon atoms and a hydroxyl group;

Q represents an amino group containing alkyl group;

m and n each represent a number of 0-3;

x represents a number of 30-400; and

y represents a number of 1-30

with an anionic group polymer, and then (2) neutralizing a reactionproduct of step (1) with an alkaline compound for a neutralization ratioof 60-150%.

The amino group containing polysiloxane of this invention is a polymerexpressed by the above chemical formula and A, R, Q, m, n, x and y aredefined as in the above formula and the numerical scope is as set forthin the above formula. When an amino group containing polysiloxaneoutside the range set forth in the above formula is employed, thecopolymer complex formed by reacting with anionic polymer forms aprecipitate in the solution, which is not desirable for this invention.

The anionic polymer useful in this invention, is illustrated by thefollowing polymers:

1-ethenyl-2-pyrrolidinone, homopolymer

1-ethenyl-2-pyrrolidinone, copolymer with acetic acid, ethenyl ester

ethene, methoxy-, copolymer with but-2-ene-l,4-dioic acid acid monoethyl or mono butyl ester

acetic acid, ethenyl ester, homopolymer carboxylated

2-butenoic acid, copolymer with acetic acid, ethenyl ester

2-butenoic acid, copolymer with alkyl 2-methyl-2-propenoate

diacetone acrylamide, copolymer with alkyl 2-propenoate or with alkyl2-methyl-2-propenoate or with 2-propenoic acid or with2-methyl-2-propenoic acid

1-(hydroxymethyl)-5,5-dimethyl hydantoin, homopolymer

In a preferred embodiment of the present invention the anionic polymeris a carboxylate group containing polymer.

The copolymer complex of this invention prepared by reacting 100 partsby weight of the amino group containing organopolysiloxane with 20 partsby weight to 5,000 parts by weight of the anionic polymer.

If less than 20 parts by weight of anionic polymer are employed, thehair set retaining property is insufficient and if more than 5,000 partsby weight of anionic polymer are used, the hair cosmetic material doesnot impart hair gloss, smooth touch, ease of combing and flexible,non-stiff finish.

The copolymer complex of the amino group containing organopolysiloxanewith the anionic polymer of this invention are neutralized with analkaline compound for a neutralization ratio of 60% to 150%.

Illustrative alkaline compounds that can be employed in this inventioninclude 2-amino-2-methyl propanol, 2-amino-2-methyl-1,3-propanediol andtriisopropanol amine.

If the neutralization ratio is less than 60%, the polymer complex doesnot dissolve into the solution, and if more than 150% of theneutralization ratio is used, the hair cosmetic material exhibits poorhair set retaining properties and gives hair sticky or starchy feeling.

The hair cosmetic material of this invention employs the above-describedpolymer complex as a main component, and can additionally employ acarrier component comprising a lower alcohol or mixture of water with alower alcohol and so that the complex can be applied in the form ofspray, aerosol, liquid or mousse.

The hair cosmetic material which is applied to the hair, according tothis invention, is prepared by blending the above described complex withone or more of the following: an oil which is used as a component of theusual hair cosmetics (camellia oil, rapeseed oil, sesame oil, saffloweroil, cottonseed oil, castor oil, soybean oil, coconut oil, palm oil,beeswax, montanic wax, lanolin, squalane, silicone oil, etc.), a surfaceactive agent (alkyl benzenesulfonate, polyoxyalkylene alkylsulfateester, alkylsulfate ester, alkanesulfonate, alkyl ethoxycarboxylate,succinic derivatives, alkylemine oxide, imidazoline compounds,polyoxyethylene alkyl or alkenyl ether, polyoxyethylene alkyl phenylether, higher fatty acid alkanolamide or its alkylene oxide additionproducts, etc.), high-molecular compounds (hydroxyethyl cellulose,hydroxypropyl cellulose, hydroxypropyl methyl cellulose, methylcellulose), antioxidants, UV absorbers, moisture retaining agents,perfumes, dyes, pigments, coloring matters, preservatives, vitamins,hormones, deodorants, binders, etc.

The hair cosmetic material of this invention is used for a variety ofhair, including artificial hair, human hair as well as an animal fur andfeathers of pets such as, for example, dogs, cats, monkeys, macaws, andcanaries.

EXAMPLES

Following are examples of this invention. (Examples of synthesizing thepolymer complex)

Synthesis--Example 1

Twenty-four (24) parts by weight of an anionic polymer (PLASCIZE L-53,available from UJI Chemical), a diacetone acrylamide copolymer withalkyl 2-propenoate 50% solution in ethyl alcohol was added to eighty(80) parts by weight of ethyl alcohol and agitated at room temperature.

Three (3) parts by weight of an amino group containing polysiloxaneexpressed by following chemical formula was added to the above mixtureand agitated at room temperature. ##STR1##

The resulting mixture was refluxed for three (3) hours at eighty (80)degrees Centigrade under a nitrogen gas atmosphere with agitation todistill the solvent (ethanol) and to obtain fifteen (15) parts by weightsolid in mixture.

The reaction product so obtained was neutralized with2-amino-2-methylpropanol for a neutralization ratio of 70% underagitation to obtain polymer complex (1).

Synthesis--Example 2

Twenty-four (24) parts by weight of an anionic polymer, (PLASCIZE L-53available from UJI Chemical), a diacetone acrylamide copolymer withalkyl 2-propenoate 50% solution in ethyl alcohol was added to eighty(80) parts by weight of ethyl alcohol and agitated at room temperature.

Three (3) parts by weight of an amino group containing polysiloxaneexpressed by following chemical formula was added to above mixture andagitated at room temperature. ##STR2##

The resulting mixture was refluxed for three (3) hours at eighty (80)degrees Centigrade under a nitrogen gas atmosphere with agitating todistill the solvent (ethanol) and to obtain fifteen (15) parts by weightsolid in mixture.

The reaction product so obtained was neutralized with2-amino-2-methylpropanol for a neutralization ratio of 70% underagitation to obtain polymer complex (2).

Synthesis--Example 3

Twenty-four (24) parts by weight of an anionic polymer (PLASCIZE L-53,available from UJI Chemical), diacetone acrylamide copolymer with alkyl2-propenoate 50% solution in ethyl alcohol was added to eighty (80)parts by weight of ethyl alcohol and agitated at room temperature.

Three (3) parts by weight of an amino group containing polysiloxaneexpressed by following chemical formula was added to above mixture andagitated at room temperature. ##STR3##

The resulting mixture was refluxed for three (3) hours at eighty (80)degrees Centigrade and under a nitrogen gas atmosphere with agitating todistill the solvent (ethanol) to obtain fifteen (15) parts by weightsolid in mixture.

The reaction product so obtained was neutralized with2-amino-2-methylpropanol, 3-propandiol for a neutralization ratio of 70%under agitation to obtain polymer complex (3).

Synthesis--Example 4

Twenty-four (24) parts by weight of anionic polymer (PLASCIZE L-53)available from UJI Chemical), an diacetone acrylamide copolymer withalkyl 2-propenoate 50% solution in ethyl alcohol was added toseventy-three (73) parts by weight of ethyl alcohol and agitated at roomtemperature.

Three (3) parts by weight of an amino group containing polysiloxaneexpressed by following chemical formula was added to above mixture andagitated at room temperature. ##STR4##

The resulting mixture was refluxed for three (3) hours at eighty (80)degrees Centigrade under a nitrogen gas atmosphere with agitating todistill the solvent (ethanol) and to obtain fifteen (15) parts by weightsolid in mixture.

The reaction product so obtained was neutralized with2-amino-2-methylpropanol for a neutralization ratio of 70% underagitation to obtain polymer complex (4).

Example 1

A hair cosmetic having the following composition was prepared:

    ______________________________________                                        Polymer complex (1)                                                                           10 parts by weight                                            Ethanol         30 parts by weight                                            Water           Balance of 100 parts by weight                                Perfume         0.1 parts by weight                                           Preservative    0.01 parts by weight                                          ______________________________________                                    

Comparative Example 1

A hair cosmetic was prepared by replacing polymer complex (1) of Example1 with the amino group containing polysiloxane used in Synthesis Example1.

This Comparative Example 1 was performed to obtain the standardevaluation of hair cosmetic of this invention, because amino groupcontaining polysiloxanes are known to give hair excellent gloss, smoothtouch, ease of combing and a flexible, non-stiff finish.

    ______________________________________                                        Amino polysiloxane                                                                              10 parts by weight                                          (used in Synthesis Example 1)                                                 Ethanol           30 parts by weight                                          Water             Balance of 100 parts by weight                              Perfume           0.1 parts by weight                                         Preservative      0.01 parts by weight                                        ______________________________________                                    

Comparative Example 2

A hair cosmetic was prepared by replacing polymer complex (1) of Example1 with the anionic polymer used in Synthesis Example 1.

This Comparative Example 2 was done to obtain the standard evaluation ofhair cosmetic of this invention, because an anionic polymers are knownto give hair good hair set retaining ability.

    ______________________________________                                        Anionic polymer   10 parts by weight                                          (used in Synthesis Example 1)                                                 Ethanol           30 parts by weight                                          Water             Balance of 100 parts by weight                              Perfume           0.1 parts by weight                                         Preservative      0.01 parts by weight                                        ______________________________________                                    

Evaluation of Example 1

GLOSS: Excellent gloss was observed comparable to that of ComparativeExample 1.

HAIR SET RETAINING: Excellent hair set retaining was observed comparableto that of Comparative Example 2.

SMOOTHNESS: Excellent smoothness was observed comparable to that ofComparative Example 1.

WETNESS: Excellent wetness was observed comparable to that ofComparative Example 1.

Example 2

A hair cosmetic having a composition prepared by replacing polymercomplex (1) of Example 1 with polymer complex (2) synthesized bySynthesis Example 2. The composition was as follows:

    ______________________________________                                        Polymer complex (2)                                                                           10 parts by weight                                            Ethanol         30 parts by weight                                            Water           Balance of 100 parts by weight                                Perfume         0.1 parts by weight                                           Preservative    0.01 parts by weight                                          EVALUATION: Good results were observed comparable to                          that of Example 1.                                                            ______________________________________                                    

Example 3

A hair cosmetic having a composition prepared by replacing polymercomplex (1) of Example 1 with polymer complex (3) synthesized bySynthesis Example 3. The composition was as follows:

    ______________________________________                                        Polymer complex (3)                                                                           10 parts by weight                                            Ethanol         30 parts by weight                                            Water           Balance of 100 parts by weight                                Perfume         0.1 parts by weight                                           Preservative    0.01 parts by weight                                          EVALUATION: Good results were observed comparable to                          that of Example 1.                                                            ______________________________________                                    

EVALUATION: Good results were observed comparable to that of Example 1.

Comparative Example 3

In accordance with the procedure set forth in Synthesis Example 1, twotests were conducted by changing the neutralization ratio from 70% to50% and 170%, respectively, using the same product obtained by reactingamino-polysiloxane with anionic polymer defined in Synthesis Example 1.

EVALUATION:

Hair cosmetic using 50% neutralization ratio

polymer complex: A precipitate was observed after three months frompreparation of this hair cosmetic. Bad storage stability.

Hair cosmetic using 170% neutralization ratio

polymer complex: Bad hair set retaining and sticky to the touch.

Example 4

A hair cosmetic having the following composition was prepared byreplacing polymer complex (1) of Example 1 with polymer complex (4)synthesized by Synthesis Example 4.

    ______________________________________                                        Polymer complex (4)                                                                           10 parts by weight                                            Ethanol         30 parts by weight                                            Water           Balance of 100 parts by weight                                Perfume         0.1 parts by weight                                           Preservative    0.01 parts by weight                                          EVALUATION: Good results were observed comparable to                          that of Example 1.                                                            ______________________________________                                    

These examples illustrate that the combination of an amino groupcontaining polysiloxane with an anionic polymer provided a hair cosmeticmaterial which is comparable or superior in gloss, wetness, ease ofcombing and in addition, imparts in hair set retention without thereaction product forming an undesirable precipitate.

What is claimed is:
 1. A hair set retaining cosmetic material comprisinga reaction product prepared by:(1) reacting for at least three hours ina solvent at the reflux temperature of the solvent(A) 100 parts byweight of an amino group containing polysiloxane expressed by thefollowing general formula:

    A.sub.m R.sub.3-m SiO(R.sub.2 SiO).sub.x (QRSiO).sub.y SiR.sub.3-n A.sub.n

whereinA is selected from the group consisting of a hydroxyl group, analkoxy group, and an amino containing alkyl group; R is selected fromthe group consisting of an alkyl group having 1 to 18 carbon atoms; Qrepresents an amino group containing alkyl group; m and n each representa number of 0-3; x represents a number 300-400; and y represents anumber of 1-30; with (B) 20 to 5,000 parts by weight of an anionic groupcontaining polymer selected from the group consisting of1-ethenyl-2pyrrolidinone, homopolymer; 1-ethenyl-2-pyrrolidinone,copolymer with acetic acid, ethenyl ester; ethene, methoxy-, copolymerwith but-2-ene-1,4 dioc acid mono ethyl or mono butyl ester; aceticacid, ethenyl ester, homopolymer carboxylated; 2-butenoic acid,copolymer with acetic acid, ethenyl ester; 2-butenoic acid, copolymerwith acetic, alkyl 2-methyl-2-propenoate; diacetone acrylamide,copolymer with alkyl 2-propenoate or with alkyl 2-methyl-2propenoate orwith 2-propenoic acid or with 2-methyl-2-propenoic acid; and1-(hydroxymethyl)-5,5-dimethyl hydantoin, homopolymer; (2) concentratingthe reaction product of step (1) to obtain a solid mixture; and (3)neutralizing the reaction product of step (2) with an alkaline compoundto a neutralization ratio of 60-150%.
 2. A process for making a hair setretaining cosmetic material comprising:(1) reacting for at least threehours in a solvent at the reflux temperature of the solvent(A) 100 partsby weight of an amino group containing polysiloxane expressed by thefollowing general formula:

    A.sub.m R.sub.3-m SiO(R.sub.2 SiO).sub.x (QRSiO).sub.y SiR.sub.3-n A.sub.n

whereinA is selected from the group consisting of a hydroxyl group, analkoxy group, and an amino containing alkyl group; R is selected fromthe group consisting of an alkyl group having 1 to 18 carbon atoms; Qrepresents an amino group containing alkyl group; m and n each representa number of 0-3; x represents a number 300-400; and y represents anumber of 1-30; with (B) 20 to 5,000 parts by weight of an anionic groupcontaining polymer selected from the group consisting of1-ethenyl-2-pyrrolidinone, homopolymer; 1-ethenyl-2-pyrrolidinone,copolymer with acetic acid, ethenyl ester; ethene, methoxy-, copolymerwith but-2-ene-1,4 dioc acid mono ethyl or mono butyl ester; aceticacid, ethenyl ester, homopolymer carboxylated; 2-butenoic acid,copolymer with acetic acid, ethenyl ester; 2-butenoic acid, copolymerwith alkyl 2-methyl-2-propenoate; diacetone acrylamide, copolymer withalkyl 2-propenoate or with alkyl 2-methyl-2-propenoate or with2-propenoic acid or with 2-methyl-2-propenoic acid; and1-(hydroxymethyl)-5,5-dimethyl hydantoin, homopolymer; (2) concentratingthe reaction product of step (1) to obtain a solid mixture; and (3)neutralizing the reaction product of step (2) with an alkaline compoundto a neutralization ratio of 60-150%.
 3. A composition according toclaim 1 wherein the reaction product os step (2) is neutralized with analkaline compound selected from the group consisting of:2-amino-2-methyl propanol, 2-amino-2-methyl-1,3-propanediol andtriisopropanol amine.
 4. A composition according to claim 1 additionallycomprising a cosmetic additive selected from the group consisting of:camellia oil, rapseed oil, sesame oil, safflower oil, cottonseed oil,castor oil soybean oil, coconut oil, palm off, beeswax, montanic wax,lanolin, squalane, silicone oil.
 5. A composition according to claim 1additionally comprising a surface active agent.
 6. A compositionaccording to claim 1 wherein the solvent is ethanol and the refluxtemperature is eighty degrees centigrade.
 7. A composition according toclaim 1 wherein the reaction product of step (1) is neutralized beforeit is concentrated.
 8. A process according to claim 2 wherein thereaction product of step (2) is neutralized with an alkaline compoundselected from the group consisting of: 2-amino-2-methyl propanol,2-amino-2-methyl-1,3-propanediol and triisopropanol amine.
 9. A processaccording to claim 2 additionally comprising the step of adding acosmetic additive selected from the group consisting of: camellia oil,rapseed oil, sesame oil, safflower oil, cottonseed oil, castor oilsoybean oil, coconut oil, palm oil, beeswax, montanic wax, lanolin,squalane, silicone oil.
 10. A process according to claim 2 additionallycomprising the step of adding a surface active agent.
 11. A processaccording to claim 4 wherein the solvent is ethanol and the refluxtemperature is eighty degrees centigrade.
 12. A process according toclaim 2 wherein the reaction product of step (1) is neutralized beforeit is concentrated.